Oiled-face adherable, hot-melt adhesive composition and a non-slip processing method of metal scaffolding board

ABSTRACT

The invention provides oiled-face adherable, hot-melt adhesive composition which has constitutive components consisting of thermoplastic resin such as ethylene-acrylate ester resin, tacky resin such as rosin ester derivative and waxes such as paraffin wax and/or plasticizer such as naphthene oil, and also contains modified resin components obtained by introducing into the molecular chains of these components a phosphoric acid group or, if desired, a carboxyl or its anhydride group, for example, by grafting 2-hydroxy-3-(meth)acryloxypropyl phosphate. 
     By providing the composition, adhesion and seal of metals with difficulty adhesive plastics are improved and a non-slip processing method of face-oiled metal scaffolding boards can be accomplished.

BACKGROUND OF THE INVENTION

1. a) Field of the Invention

The present invention relates to a hot-melt type adhesive compositionwhich is suitable for adhesion and sealing to metals withoutpretreatment and a non-slip processing method of metal scaffoldingboard.

More particularly, the invention relates to the hot-melt adhesivecomposition which can be preferably used for adhesion of plastics havingdifficulty on adhesion and sealing to metals, is excellent in adhesionproperties to oiled surface of metals, resistance to water andcorrosion, and is capable of conducting instant adhesion or short timeadhesion. And the invention relates to the non-slip processing method ofmetal scaffolding board by using oiled-face adherable hot-melt adhesivewithout pretreatment.

2. b) Description of the Invention

A hot-melt adhesive composition having 100% solid content hasconventionally been used in various fields, well known on its usefulnessin industry, and employed in a rapidly increasing amount due to instantadhesion characteristic and freedom pollution.

Conventional arts for adhesives exhibiting adhesion properties to oiledsurface have been known as thermosetting type adhesives, for example, anepoxy adhesive, solvent type adhesive and a two component acrylicadhesive. These adhesives substantially have problems of toxicity, odorand poor workability and hence conversion to a solventless type hot-meltadhesive composition is required.

However, a hot-melt adhesive which exhibits good adhesion properties toboth the oiled surface of metals and non-polar plastics has not yet beenfound.

In the field of automotive assembly, particularly reliability inadhesion is regarded as important for the adhesion processing of steelplates or adhesion of various plastic parts for rigging. A liquid epoxyadhesive capable of oiled-face adhesion is used for the adhesion offace-oiled steel plates in a door hemming portion.

Hot-melt adhesives have recently been focused attention again for theadhesion of various plastic parts for rigging in view of pollution-freeproperties and increase in productivity. However, adhesives which canexhibit satisfactory adhesion properties to face-oiled materials havenot yet been found.

In the field of building materials, for example, hot-melt adhesive isalso coated on metallic scaffold plates in order to prevent slip.However, conventional adhesives can be applied to degreased materialsalone and require complex coating steps. Development of hot-meltadhesive composition capable of adhering to oiled surface is stronglydesired in view of pollution-free application and energy saving.

A hot-melt adhesive composition primarily composed of butyl rubber hasbeen disclosed in Japanese Patent Publication 92379 (1985) as apollution-free, instant adhesive or an adhere-sealing agent which ismost suitable for plastics of difficult adhesion. Some of other hot-meltadhesive compositions have been known to contain thermoplastic macromolecule such as styreneethylene-butylene-styrene resin,styrene-butadienestyrene resin, and styrene-isoprene-styrene resin as abase polymer and other components such as tackifiers, waxes andplasticizers.

For adhesion of woods and papers in particular, many hot-melt adhesivecompositions containing ethylenevinyl acetate resin as thermoplasticmacro molecule have been known. On the other hand, disclosed arts forhot-melt adhesive compositions capable of adhering metals includepolyamide base, polyester base, ethylene-vinyl acetate base and rubberbase hot-melt compositions. Any of these adhesive compositions, however,have exhibited adhesion reliability only on a clean surface of metals.Oiled metal surface having build-up of cutting oil, lubricant or rustproof oil can not at all or scarcely exhibit adhesive force as such bythe conventional hot-melt adhesive composition.

Consequently, in the case of adhering metals by using conventionallyknown hot-melt adhesive compositions, it has been required, for example,to previously conduct degreasing treatment, or to carry out flametreatment for degreasing and preheating, or to use a specific primer.

As mentioned above, there are following four requirements in the market.

The first requirement is to provide a hot-melt adhesive compositionhaving excellent adhesion to oiled surface without pretreatment byutilizing instant adhesion properties of the hot-melt adhesive.

The second requirement is to provide reliability for adhesion to, forexample, polypropylene, acrylics, polyethylene, polycarbonate,acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin andother plastics which are difficult to adhere.

The third requirement is to provide the adherend with water resistanceand environmental compatibility.

The fourth requirement relates to the above third requirement, and is toprovide rust prevention for metals, that is, to provide a hot-meltadhesive composition having high rust-preventive effect after adhesion.

SUMMARY OF THE INVENTION

The object of the invention is to obtain a hot-melt adhesive compositionwhich is, in adhesion of metallic materials, suitable for carrying outadhesion without pretreatment under high reliability and capable ofconducting pollution-free and instant adhesion. That is, the object isto provide a composition which can instantly adhere the metal surfacestained with machine oil, lubricant, rust preventing oil, grinding oil,processing oil and other residual oils used for machining treatment ofthe metal surface.

Another object of the present invention is to provide a hot-meltadhesive composition which exhibits reliability on adhesion-sealing,water resistance and rust prevention of metals for a long period.

Another object of the present invention is to provide a non-slipprocessing method of a metal scaffolding board by using oiled-faceadherable hot melt adhesive composition.

As a result of an intensive research in order to solve the aboveproblems, the present inventors have found that in a hot-melt adhesivecomposition containing a required component composed of a thermoplasticbase polymer and a tackifier and an optional component composed of a waxand a plasticizer, the above object can be accomplished by providing amodified resin obtained by introducing a phosphoric acid group into amolecular chain in one of the above constitutive components. Thus thepresent invention has been completed.

That is, the aspect of the present invention is an oiled-face adherable,hot-melt adhesive composition having constitutive components comprisingof a thermoplastic base polymer, tackifier and one or more of additiveselected from the group consisting of waxes and plasticizers, one ormore of molecular chain in said constitutive components comprising amodified resin component obtained by introducing into a molecular chaina functional group represented by the formula (I): ##STR1## wherein R₁is a hydrogen atom, an alkyl group having from 1 to 8 carbon atoms,##STR2## R₂ is a hydrogen atom, methyl group, ·NH₄ or ·NH₃ --CH₂ --CH₂OH; R₃ is a hydrogen atom or a methyl group; A is ##STR3## m is aninteger of 2 or 3; R₄ is a hydrogen atom or a methyl group; R₅ is ahydrogen atom, methyl group, hydroxymethyl group or a chloromethylgroup; X is --P--(OH)_(2;) and Y is an integer of from 1 to 15.

DETAILED DESCRIPTION OF THE INVENTION

The oiled-face adherable, hot-melt resin composition of the presentinvention described above has preferably following embodiments.

That is, the composition of the invention is a hot-melt adhesive havingconstitutive components comprised of at least a thermoplastic basepolymer and a tackifier and optionally a wax and/or a plasticizer.Preferred composition comprises in a molecular chain of at least one ofthe constitutive components a phosphoric acid group or a half amine saltgroup which are represented by the above formula (I) and furthercomprises one or more of functional groups selected from --COOH and##STR4## which are introduced into the same or different molecularchain.

A more preferred composition comprises a modified resin componentobtained by grafting unsaturated carboxylic acid or its anhydride in anamount of 5% by weight or less. A more preferred composition comprises,as the tackifier, hydrogenated rosin, a hydrogenated rosin esterderivative or polymerized rosin in the range of from 1 to 40% by weight.A more preferred composition comprises a modified resin componentobtained by grafting from 0.1 to 20 parts by weight of a compoundselected from the group consisting of 2-hydroxy-3-(meth)acryloxypropylphosphate, 2-hydroxy-3-(meth)acryloxyethyl phosphate and their halfamine salts into 100 parts by weight of the constitutive components.

A more preferred composition comprises a modified resin componentobtained by reacting a resin component having a hydroxyl group with anagent selected from the group consisting of phosphorus pentoxide,phosphorus trichloride and phosphorus oxychloride and hdyrolyzing theresultant intermediate.

A more preferred composition comprises a modified resin componentobtained by introducing a glycidyl group into the constitutivecomponents and successively reacting the resultant intermediate withphosphorous acid or phosphoric acid.

A more preferred composition comprises one or more of thermoplasticresin having a molecular weight in the range of from 20,000 to 1,000,000and selected from the group consisting ofstyrene-ethylene-butylene-styrene resin, styrene-ethylene-butyleneresin, styrene-ethylene-propylene-styrene resin, ethylenepropylene resinand ethylene acrylate ester resin; and the thermoplastic resinpreviously comprises both or either of the modified resin componentsobtained by (A) grafting from 1 to 20 parts by weight of a compoundselected from the group consisting of 2-hydroxy-3-(meth)acryloxypropylphosphate, 2-hydroxy-3-(meth)acryloxyethyl phosphate and an half aminesalt of these phosphates upon 100 parts by weight of the thermoplasticresin, and (B) grafting from 0.1 to 5 parts by weight of a monomerselected from the group consisting of maleic anhydride, acrylic acid andmethacrylic acid.

The most preferred composition is a hot-melt adhesive composition havingconstitutive components composed of:

(a) from 5 to 80% by weight of one or more of thermoplastic base polymerhaving a molecular weight of from 20,000 to 1,000,000 and selected fromthe group consisting of butyl rubber, polyisobutylene,styrene-butadienestyrene resin, styrene-isoprene-styrene resin,styreneethylene-butylene-styrene resin, styrene-ethylenebutylene resin,styrene-ethylene-propylene-styrene resin, ethylene-propylene resin,ethylene-vinyl acetate resin and ethylene-acrylate ester resin,

(b) from 20 to 60% by weight of one or more of tackifier selected fromthe group consisting of a hydrogenated terpene base resin, hydrogenatedpetroleum resin, hydrogenated alicyclic base petroleum resin and a rosinester derivative resin,

(c) from 1 to 20% by weight of one or more of wax selected from thegroup consisting of paraffin base wax, polyethylene base wax,polypropylene base wax and modified wax thereof, and

(d) from 0 to 30% by weight of one or more of plasticizer selected fromthe group consisting of liquid polybutene, liquid hydrogenatedpolyisprene and atactic polypropylene; and these constitutive componentscomprise a modified resin component obtained by grafting from 1 to 20parts by weight of 2-hydroxy-3-(meth)acryloxypropyl phosphate or2-hydroxy-3-(meth)acryloxyethyl phosphate into 100 parts by weight ofthe sum of the thermoplastic base polymer, tackifier and one or more ofother constitutive components.

Further, the present invention is a non-slip processing method of ametal scaffolding board comprising conducting hot-melt coating of theabove oiled-face adherable, hot-melt adhesive composition on the backsurface of the metal scaffolding board without surface treatment to forma non-slip film composed of one or a plurality of layer having a widthof from 5 to 30 mm.

The preferred embodiments for the above non-slip processing method ofthe metal scaffolding board is to form a plurality of coated layer andto apply wet-on-wet to the second or the upper layer, simultaneouslywith the first layer or separately, a non-polar hot-melt compositionconsisting essentially of from 20 to 60% by weight of an ethylene-vinylacetate resin or an ethyleneacrylate ester resin, from 75 to 10% byweight of a tackifier having a softening point of from 80° to 130° C.and from 5 to 30% by weight of a wax.

The present invention will hereinafter be described in detail.

The oiled-face adherable, hot-melt adhesive composition of the inventioncontains a modified resin component obtained by chemically introducinginto the molecule of one or more of the constitutive components in thehot-melt adhesive a functional group represented by the formula (I),that is, a phosphoric acid group having at least one -P-OH bond,phosphorous acid group, phytic acid group or half amine salts of thesegroups.

That is, the hot-melt adhesive composition contains a modified resincomponent obtained by chemically introducing the phosphoric acid groupinto one or more of the components selected from the below describedthermoplastic base polymer, tackifier and wax and/or plasticizer;preferably contains a modified resin component obtained by chemicallyintroducing the phosphorous acid group or the phosphoric acid groupcorresponding to the range of from 0.01 to 20% by weight converted tophosphoric acid; most preferably contains a modified resin componentobtained by further introducing a carboxyl or its anhydride group intothe same or different molecule of the above component modified with thephosphoric acid group, thereby subjected to coexist two kinds offunctional groups.

The fundamental constitution of the hot-melt adhesive composition of theinvention is composed of a so-called thermoplastic base polymer,tackifier and wax and/or plasticizer.

The hot-melt adhesive composition of the invention preferably containsthe thermoplastic base polymer described below.

The number average molecular weight of the base polymer measured byhigh-performance liquid chromatography is in the range of from 20,000 to1,500,000, preferably from 20,000 to 1,000,000 more preferably from20,000 to 500,000.

The thermoplastic base polymer is preferably compatible with the belowdescribed tackifier and wax components. No particular restriction isimposed on the base polymer. Exemplary thermoplastic base polymerincludes butyl base rubber, partially crosslinked butyl rubber,polyisobutylene resin, styrene-ethylene-butylene resin,styrene-ethylene-butylene-styrene base block copolymer,styrene-ethylene-propylene base block copolymer,styrene-isoprene-styrene base block copolymer, styrene-butadiene-styrenebase copolymer, ethylenepropylene base resin, acrylic rubber, polyesterresin, modified high molecular weight polyethylene having a melt indexof from 5 to 200 g/10 min at 180° C., ionomer resin, ethylene-acrylateester copolymer having an acrylate ester content of from 1 to 45% and amelt index of from 0.1 to 750 g/10 min at 180° C., polyamide resin,polyimide resin and polycarbonate resin.

These thermoplastic base polymer are used singly or as a mixture in anamount of from 5 to 45% by weight and preferably used as a mixture of 5kinds or less.

Combined use of at least 2 kinds of resin selected from butyl rubber,styrene-ethylene-butylene-styrene resin, styrene-ethylene-butyleneresin, styreneethylene-propylene-styrene resin, ethylene-propylene resinand ethylene-acrylate ester resin is preferred in view of heat stabilityand adhesion characteristics.

The above resin can be used for the thermoplastic base polymer to bemodified by introducing the phosphoric acid group and, if desired, thecarboxyl or its anhydride group into the molecule. Thus modification canbe readily carried out and the resultant modified resin component canpreferably provides the oil-face, adherable, hot-melt adhesivecomposition of the invention which has suitable rigidity and toughnessand is also excellent in weatherability and heat stability.

In the oiled-face adherable hot-melt adhesive composition of theinvention, no particular restriction is placed on the total amount ofthe thermoplastic base polymer which partially includes the modifiedbase polymer obtained by introducing into the molecule the abovephosphoric acid group and, if desired, the carboxylic acid or itsanhydride group. The total amount is generally from 5 to 80% by weight,preferably from 20 to 50% by weight. The total amount less than 5% byweight is liable to lack strength in high temperature. On the otherhand, the total amount exceeding 80% by weight leads to viscosityincrease in the hot-melt adhesive and thereby tends to decrease coatingworkability and to cause poor wetting properties to the target materialfor adhesion.

The coiled-face adherable, hot-melt adhesive composition of theinvention is required to use the tackifier by the following reason.

The tackifier is very effective for viscosity reduction and wettingproperty control of the hot-melt adhesive composition of the invention,in other words, for the improvement of workability, adjustment of hottack and open time control, and hence is important for the exhibition ofinstant adhesion properties.

Conventionally known tackifiers can be used for the invention.Representative tackifiers include, for example, (hydrogenated)aromaticor aliphatic petroleum resin, terpene base resin, terpene-phenolcopolymer resin, (hydrogenated)rosin and (hydrogenated)rosin ester baseresin, polymerized rosin, hydrogenated dicyclopentadiene base resin,styrene base resin, coumarone-indene resin, ketone resin, xylene resin,C-5 base petroleum resin obtained by copolymerizing C-5 fractionincluding pentene, isoprene, piperylene and 1,3-pentadiene which areformed by thermal decomposition of petroleum naphtha, C-9 base petroleumresin obtained by copolymerizing C-9 fraction including indene,vinyltoluene and α- or β-methylstyrene which are formed by thermaldecomposition of petroleum naphtha, and a petroleum resin obtained bycopolymerization of the above C-5 and C-9 fractions. These tackifiershave an average molecular weight of preferably in the range of from 400to 3000.

The total amount of the tackifier which contains, if desired, themodified tackifier obtained by introducing the above phosphoric acidgroup and the carboxyl or its anhydride group into the molecular chainis preferably 80% by weight or less, more preferably from 20 to 60% byweight, most preferably from 20 to 50% by weight of the composition. Thetackifier can be used singly or in combination.

When the introduction of the above phosphoric acid group and, ifdesired, the carboxyl or its anhydride group into the molecular chain iscarried out with a graft reaction, a tackifier which gives no adverseeffect on the graft reaction is preferably selected. A tackifier whichinhibits the reaction by converting active radical to stabilized radicalis not used for modification and preferably added after finishingmodifications.

Row material resins for the tackifier which are suitable for carryingout the introductions of the above functional groups by grafting in theinvention include, for example, hydrogenated petroleum resin,hydrogenated terpene resin, hydrogenated rosin, hydrogenated rosin esterbase resin, styrene base resin, ketone resin, xylene resin, hydrogenatedC-5 or hydrogenated C-9 base petroleum resin and hydrogenated C-5/C-9copolymer resin. On the other hand, rosin, rosin ester defivative resinand terpene-phenol copolymer resin which are thought to inhibit graftingare preferably used in a minimum amount.

However, rosin, rosin ester derivative resin and terpene-phenolcopolymer resin which have carboxyl groups or hydroxyl groups in themolecule exhibit remarkable effect for improving wetting properties tometals and are preferably added in the final stage of the grafting.

When the above phosphoric acid groups are introduced into the molecularchain of the tackifier by utilizing, for example, phosphorus pentoxide,phosphorus trichloride and phosphorus oxychloride as raw materials forintroducing the functional groups, resins having active hydroxyl groupsin the molecule are preferably selected for use. No particularrestriction is imposed upon the single use of the resin or the combineduse of a chemically inactive and unreacted (nonpolar) tackifier as adiluent. When increased generation of side reactions are anticipated incarrying out the above reaction, combined use of an inactive solvent ordilution with the non-reactive tackifier is preferred in order toconduct the reaction under mild conditions.

Wax is used for the hot-melt adhesive composition of the invention. Useof the wax enables viscosity reduction and control of wettingproperties, i.e., enhancement of workability, inhibition of blocking,control of open time and remarkable improvement of heat resistance. Thusfavorable properties for instant adhesion can be exhibited.

Exemplary wax for use in the invention includes polyethylene base wax,polypropylene base wax, paraffin wax, microcrystalline wax, naturalwaxes and modified products of these waxes.

The total amount of the wax which contains, if desired, so-calledmodified wax obtained by introducing the above phosphoric acid group andthe carboxylic or its anhydride group into the molecular chain is 30% byweight or less, preferably in the range of from 1 to 20% by weight ofthe composition. The amount of more than 30% by weight makes open timetoo short and is liable to lack in workability for adhesion.

Plasticizer can be used for the hot-melt adhesive composition of theinvention. Use of the plasticizer can provide suitable rubber elasticityand remarkably improves low temperature adhesion characteristics.

Preferred plasticizers which can be used include a single compound or amixture of the compound selected from atactic polypropylene, liquidpolybutene, polyisobutylene having a molecular weight of from 5,000 to12,000, paraffin base oil, naphthalene base oil, straight chain fattyacid esters and aromatic polycarboxylic acid ester derivatives.

No particular limitation is placed upon the amount of the plasticizerused. The amount generally depends upon the heat resistance and rigidityof the hot-melt adhesive composition of the invention. The total amountof the plasticizer which contains, if desired, modified plasticizerobtained by introducing the above phosphoric acid group and the carboxylor its anhydride group into the molecular chain is preferably 50% byweight or less, more preferably from 5 to 30% by weight of thecomposition in view of the balance of properties such as low temperatureadhesion, open time and blocking. Use of the plasticizer exceeding 50%by weight is liable to be too much plasticized and causes problems onrigidity at high temperature.

The oiled-face adherable, hot-melt adhesive composition of the inventioncan be, if desired, incorporated with the following pigments, fillers,ultraviolet absorbers, ultraviolet stabilizers, antioxidants and aginginhibitors. Representative materials will be illustrated below.

Fillers have a particle size of 100 mesh or less and include, forexample, carbon black, talc, clay, silica, barium sulfate, calciumcarbonate, barium carbonate, magnesium oxide and titanium oxide. Thesefillers are generally used for paints and adhesives, and can be used inan amount of 60% by weight or less of the composition in the invention.

Exemplary ultraviolet absorbers which can be used include2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole,2-(3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole,2-(3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole,2-(3,5-di-tertbutyl-2-hydroxyphenyl)-5-chlorobenzophenol,2-(3,5-ditert-amyl-2-hydroxyphenyl)benzotriazole and other benzotriazolebase compounds; 2-ethoxy-2'-ethyloxazolic acid bisanilide,2-ethoxy-5-tert-butyl-2'-ethyloxazolic acid bisanilide and otheroxazolic acid amide base compounds; and 2,4-hydroxy-4-octoxybenzophenoneand other benzophenone base compounds. The ultraviolet absorbers can beused in an amount of from 0.1 to 3% by weight of the compound.

Ultraviolet stabilizers which can be used include, for example, hinderedamine compounds such as bis(2,2,6,6-tetramethyl-4-piperazyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sabacate, dimethylsuccinate/1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidinepolycondensate and 1-[2-{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy}ethyl]-4-[3-(3,5,-di-tert-butyl-4-hydroxyphenyl)propionyl]-2,2,6,6-tetramethylpiperidine. The ultraviolet stabilizers can be used in an amount of from0.05 to 3% by weight of the composition.

Representative antioxidants which can be used include, for example,2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine,pentaerythrityltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],2,2-thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)priopionate],octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,2,2-thio-bis(4-methyl-6-tertbutylphenol),N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-cinnamide) and otherhindered phenol base compounds; andtris(2,4-di-tert-butylphenyl)phosphite, tris(nonylphenyl)phosphite,trinonyl phosphite, tris(2-ethylhexyl)phosphite and other phosphite basecompounds. The antioxidants can be used in an amount of from 0.1 to 2%by weight of the composition.

The oiled-face adherable, hot-melt adhesive composition of the presentinvention comprises the modified resin component obtained byintroducing, as a functional group, the phosphoric acid group and, ifdesired, the carboxyl or its anhydride group into one or more molecularchains selected from the above base polymer tackifier, wax andplasticizer.

Accordingly, suitable raw materials and modification processes forproviding the above modified resin components will be describedhereinafter.

No particular restriction is put on the ethylenically unsaturatedphosphoric acid ester monomer which can be preferably used forintroducing the phosphoric acid group into the molecule. The exemplarymonomers include (meth)acryloxyalkyl phosphate base monomers such as2-hydroxy-3-methacryloxypropyl phosphate (another name: andphosphoxypropyl methacrylate), 2-hydroxy-3-methacryloxyethyl phosphate,2-hydroxy-3-acryloxypropyl phosphate, 2-hydroxy-3-acryloxyethylphosphate, 2-hydroxy-3-(γ-chloro-β-propylmethacrylate), monoethanolaminesalt of acid phosphoxyethyl methacrylate, monoethanolamine salt of acidphosphoxypropyl methacrylate, monoammonium salt of acid phosphoxyethylmethacrylate, and monoammonium salt of acid phosphoxypropylmethacrylate.

The above phosphoric acid ester monomers are reaction products and theirhalf salts of acrylate esters or methacrylate esters such as2-hydroxyethyl acrylate, 2-hdyroxyethyl methacrylate, 2-hydroxypropylacrylate and 2-hydroxypropyl methacrylate which have a hydroxyl group inthe molecule with phosphorus pentoxide, phosphorus trichloride,pyrophosphoric acid and phosphorus oxychloride.

Addition products and their half salts of phosphoric acid with glycidylacrylate or glycidyl methacrylate are also preferred monomers such asmethacryloyloxyethyl acid phosphate dimethylaminoethyl methacrylate.

Addition products and their half salts of phosphorous acid with glycidylacrylate or glycidyl methacrylate are further preferred monomers.

Still further preferred monomers are acid phosphoxypolyoxyethyleneglycol monomethacrylate and its half salts, acidphosphoxypolyoxypropylene glycol monomethacrylate and its half salts,and associated compounds of acid phosphoxypolyoxypropylene glycolmonomethacrylate with methacryloyloxyethyl acid phosphatedimethylaminoethyl methacrylate.

Addition products and their half salts of phytic acid with glycidylacrylate or glycidyl methacrylate, and vinyl monomers containing anethylenically unsaturated group and P-OH group, for example,vinylbenzene phosphoric acid are also included in the scope of thesemonomers.

In the above monomers, particularly preferred monomers for the inventionare 2-hydyoxy-3-(meth)acryloxypropyl phosphate,2-hydroxy-3-(meth)acryloxyethyl phosphate,2-hydroxy-3-(γ-chloro-β-propyl methacrylate), monoethanolamine salts ofacid phosphoxyethyl methacrylate, monoethanolamine salts of acidphosphoxypropyl methacrylate, monoammonium salt of acid phosphoxyethylmethacrylate, monoammonium salt of acid phosphoxypropyl methacrylate,methacryloxyethyl acid phosphate dimethylaminoethyl methacrylate, acidphosphoxypolyoxyethylene glycol monomethacrylate or its half salt, acidphosphoxypolyoxypropylene glycol monomethaclrylate, and associatedcompounds of acid phosphoxypolyoxypropylene glycol monomethacrylate withmethacryloyloxyethyl acid phosphate dimethylaminoethyl methacrylate.

2-Hydroxy-3-(meth)acryloxypropyl phosphate,2-hydro-3-(meth)acryloxyethyl phosphate and their primary amine additiontype half salts are preferred because of ready availability of themarket.

In order to introduce the phosphoric acid group in the invention, it ispreferred to use an additioncondensation reaction. For example, in ageneral process, phosphorous pentoxide, phosphorus trichloride,phosphorus oxychloride, phosphorous acid or its half amine salts, andphosphoric acid or its half amine salts are reacted with active hydroxylgroup or glycidyloxy group to introduce the phosphoric acid group intothe molecule.

In the first process, a prescribed amount of the above ethylenicallyunsaturated phosphoric acid ester monomer is added to a component or acombination thereof selected from the constitutive components of theabove hot-melt adhesive. Grafting of the resultant mixture was carriedout in a nitrogen atmosphere under melt-kneading by the addition of aradical generation catalyst.

Conventionally known catalysts can be used for the radical generationcatalyst. Preferred catalysts are, for example, organic peroxides, azobase initiators, and photo radical initiators.

The grafting reaction can be carried out in the absence of a solvent, orin the presence of one or more constitutive components of the inventionas a diluent or retarder of the reaction, or in the presence of a knownsolvent having good compatibility with the constitutive components orthe modified main materials of the invention and by removing the solventafter finishing the modification. Thus no particular restriction isimposed upon the grafting conditions.

Grafting is carried out generally in the range of from 80° to 200° C.,preferably from 100° to 150° C.

In the second process, active hydroxyl groups in the molecule arereacted (addition, condensation) with phosphorus pentoxide, phosphorustrichloride, phosphorus oxychloride or pyrophosphoric acid to introducethe phosphoric acid group into the molecular chain.

This process can also be applied with ease to the constitutivecomponents of the above hot-melt adhesive which have no functional groupat all by carrying out pretreatment. One or more of the constitutivecomponents having no polar functional group are previously treated withhydrogen peroxide to introduce active hydroxyl groups in the moleculeand then reacted with, for example, phosphorous pentoxide to introducethe phosphoric acid group.

When the constitutive components of the above hot-melt adhesive whichalready have carboxyl or acid anhydride groups in the molecule are usedfor the raw material of modification, active hydroxyl groups arepreviously introduced, for example, by esterifying with a known organicdiol compound or by addition of a known mono- or poly-epoxy compound andthen the above modification process can be preferably carried out.

In other words, the molecular chain is once converted to an activehydroxyl group in the second process by utilizing various chemicalreactions depending upon the kind of functional group in the resinbefore modification, and then reacted with phosphorus pentachloride toachieve the modification.

The preferred constitutive components of the above hot-melt resincomposition which already have hydroxyl groups include, for example,tackifiers such as terpene-phenol copolymer resin, terpene-bisphenolcopolymer resin, p-hydroxystyrene copolymer petroleum resin andp-hydroxy-α-methylstyrene copolmer petroleum resin; and plasticizers andwaxes such as (hydrogenated) polybutadiene monol, (hydrogenated)polybutadiene diol, (hydrogenated) polyisoprene monol, (hydrogenated)polyisoprene diol and other liquid, low molecular weight, terminalhydroxylated polyolefin resin, oxidized polyethylene wax, oxidizedpolypropylene wax and oxidized paraffin wax. These components can bereadily converted to modified resin components by the second process.

In the third process, glycidyl groups in the molecule is reacted(addition.condensation) with phosphorous acid or its half amine salts,phosphoric acid or its half amine salts, and phytic acid to obtainmodified resin.

When the constitutive components of the hot-melt adhesive which have offunctional group at all are modified by the third process, the belowdescribed pretreatment reaction is previously carried out as conductedin the second process and then glycidyl group is introduced to achievemodification

One or more of the constitutive components having no polar functionalgroup are previously grafted with an allylglycidyl ether compound,glycidyl methacrylate or glycidyl acrylate to introduce active glycidylgroups in the molecule and then phosphorous acid or phytic acid is addedto achieve modification. Namely, various known chemical reactions areutilized depending upon the kind of functional group in the resin beforemodification and active glycidyl groups are finally introduced into themolecule to carry out modification.

The reactions in the second and third processes can be carried out inthe absence of a solvent, or in the presence of one or more ofconstitutive components of the invention as a diluent, or in thepresence of a known inactive solvent having good compatibility with theconstitutive components or the modified main materials of the inventionand by removing the solvent after finishing the modification. Thus noparticular restriction is placed on conducting the reaction. Additionand condensation reactions are preferably carried out in anhydrousconditions in view of preventing side-reactions.

After finishing the reaction, a prescribed amount of water is generallyadded to the reaction mixture and the introduced group is finallyconverted to --P--OH group. When water is contained in the raw materialsto be added in the later step, addition of water can be preferablyomitted.

The reaction in the second and the third processes is carried outgenerally in the range of from 20° to 0° C., preferably from 50° to 80°C.

In the phosphoric acid introduction process of the invention usingphosphorus trichloride and phosphorus oxychloride, secondary treatments,for example, addition of HCl removing agents to increase heat stabilityof the resin, HCl elimination under high vacuum to increase heatstability of the resin, and HCl removal by hot water extraction, arealso included in the scope of the process.

The term "modified resin having a carboxyl group or its anhydride"[hereinafter referred to as (dehydrated)carboxyl group] includes acompound obtained by below described processes and a resin which isconventionally available in the market and already contains(dehydrated)carboxyl group as a functional group.

Exemplary resin which is available in the market include maleicanhydride grafted styrene-ethylene-butylene-styrene block copolymerresin and other acid modified thermoplastic base polymer; acid modifiedpolypropylene wax, acid modified polyethylene wax, acid modifiedparaffin wax and other acid modified waxes; and rosin, partiallyesterified rosin derivatives, polymerized rosin and other tackifiers.

The process for introducing the (dehydrated) carboxyl group as afunctional group includes graft reaction. Representative modifyingagents which can be most suitably used for the graft reaction include,for example, maleic acid, maleic anhydride, fumaric acid, itaconic acid,itaconic anhydride, crotonic acid, citraconic acid, citraconicanhdyride, acrylic acid and methacrylic acid. Preferred materials aremaleic anhydride, itaconic anhydride, crotonic acid, acrylic acid andmethacrylic acid. More preferred materials are maleic anhydride, acrylicacid and methacrylic acid.

The modification process utilizing the grafing reaction of the aboveunsaturated organic acids can be carried out by the same procedures asgraft introduction of the above phosphoric acid group. The process canbe conducted by simultaneously using the same radical generatingcatalyst as described in the first process and a prescribed amount ofthe above unsaturated organic acid is added in a nitrogen atmosphereunder melt·kneading. No particular limitation is put on the selection oftemperature, radical generating catalyst (radical initiator) and otherreaction conditions.

The graft modification of introducing the above (dehydrated) carboxylgroup can be carried out simultaneously, in a multi step or separatelywith the above grafting of the phosphoric acid group. The presentinvention is not restricted by the difference of modification process.

The hot-melt adhesive composition of the invention preferably containsthe resin component obtained by grafting the above unsaturated organicacid in an amount of 5% by weight or less of the constitutionalcomponents. It is also preferred in view of remarkable effect on waterresistance and rust prevention of metals to contain one or moretackifiers selected from the group consisting of (hydrogenated) rosin,partially esterified (hydrogenated) rosin derivative and polymerizedrosin in the range of from 1 to 40% by weight. The effect on waterresistance is not increased even though the amount exceeds 5% by weight.The amount exceeding 40% by weight decreases heat stability. The amountless than 1% by weight has almost no effect. Hence the above range ispreferred.

In the hot-melt adhesive composition of the invention, that theconstitutive components contain modified resin obtained by introducingthe phosphoric acid group into one or more molecular chain, and morepreferably that the components simultaneously contain the(dehydrated)carboxyl group, are requirements for exhibiting desiredproperties of oiled-face adhesive and conducting strong adhesion withoutpreheating.

Such remarkable effect is assumed to result from strong affinity of thephosphoric acid group to metal surface.

The hot-melt adhesive composition of the invention is preferred inconclusion to have low melt viscosity in view of obtaining sufficientlyhigh oiled-face adhesion and good workability in coating operation. Meltviscosity at 200° C. is generally 200,000 cps or less, preferably100,000 cps or less, most preferably in the range of from 500 to 50,000cps.

When the hot-melt adhesive composition has good viscosity behavior,i.e., flow property, wetting is rapidly performed on the adherendsurface and remarkable effect can be exhibited on the adhesion of acoarse and oiled surface.

The preparation of the composition in the present invention ispreferably carried out by using a strong stirr-mixer such as apolymerization vessel or a Banbury type kneader. The grafting reactionor chemical modification under melt-mixing state can be conducted byheating in a nitrogen atmosphere. The modification and the kneadingprocedures may be conducted separately, in multiple steps orsimultaneously. Any procedures can be suitably employed.

In the preferred preparation process of the invention, the phosphoricacid group or the (dehydrated) carboxyl group are respectivelyintroduced in advance by the above processes, the constitutivecomponents of the invention are further added, and successively, ifdesired, fillers, ultraviolet absorbers, ultraviolet stabilizers,antioxidants (aging inhibitors), surface active agents, pigments andvarious coupling agents are further added, and the resulting mixture isthoroughly melt-kneaded to obtain the hot-melt adhesive composition ofthe invention.

No particular restriction is imposed upon the order of formulation andthe order of the addition in the modificaltion process. It is preferredto select means which can inhibit deterioration and abnormal phenomenonof effective components.

No particular limitation is placed on the morphology of productsprepared by the oiled-face adherable, hot-melt adhesive composition ofthe invention. For example, films, pellets, blocks, tapes, bars, cannedpackages and other optional shapes can be employed.

No particular restriction is imposed upon the coating method or theadhesion-sealing method using the hot-melt adhesive composition of theinvention. Suitably employed methods are, for example, coating orsealing methods such as bead coating, area coating and spot coatingwhich use various hot-melt applicators, multiple coating.adhesionmethod, clamping adhesion with hot or cold rolls, clamping adhesion withexclusive jigs, press adhesion and other arbitrary adhesion fixingmethods.

EXAMPLE

The present invention will hereinafter be illustrated by way of examplesHowever, scope of the invention is not limited by the specificembodiments. Proportion of each component in the examples is indicatedby parts by weight.

Testing materials

The surface-treated steel plates used for the oiled-face adhesion testdescribed in the examples were prepared by the following method.

An SPCC steel plate having a thickness of 0.5 mm and width of 25 mm wassubmerged in a press oil, taken out and allowed to stand for 10 minutesat a vertical position, followed by submerging in a rust-prooflubrication oil, taken out and allowed to stand for 24 hours at avertical position to remove excess oil.

Another SPCC steel plate which was already subjected to rust-prooflubricating oil treatment was purchased from a test panel supplier andused as such for the test.

Steel plates such as galvanized sheet iron and SPCC steel plate weresubmerged in an aqueous emulsion type lubricant containing naturalvegetable oil, mineral oil and a glycol derivative as main components,taken out and then water was removed with an air spray gun to obtain atest specimen.

Heat stability test

The heat stability test of the hot-melt adhesive composition in theexamples was carried out by charging 100 g of the composition into a 200ml glass beaker, heating in an oven for a predetermined time andthereafter measuring changes in appearance, viscosity and properties.

Rust-preventing durability test

The rust-preventing durability test of the hot-melt adhesive compositionin the examples was carried out by coating on a steel plate in athickness of about 20 to 30 μm, allowing to stand for a week, followedby giving the coated film a cross-cut to the depth of metal surface atthe center of the specimen by using a sharp cutter knife, dipping alower half of the resulting specimen in city water or in a 4% aqueoussodium chloride solution at 40° C. so as to expose an upper half of thespecimen into the air, allowing to stand for 3 days, and taking out toobserve rust generation on the metal surface and changes in coated filmadhesion

Non-slip processing test

A galvanized sheet iron was drilled at the portion corresponding to thetop of a scaffolding board. Under pouring a sufficient amount ofcoconut-oil-base lubricant on the processing rolls, the perforated sheetiron obtained above was continuously passed through the rolls to processinto a shape of the scaffolding board having a section composed of 20 cmin width, 3.5 cm in height of channel type both sides and 2 cm in widthof both bottom portions and having a length of 2 m.

Then, turning the scaffolding board upside down, dehydration was carriedout by blowing the air at high pressure of 2 to 6 kg/cm². On both edgesof the back surface of the scaffolding board which surface was still inan oil-stained state, non slip processing was carried out at a coatingline speed of 5 m/min or 15 m/min by using a gear pump type hot-meltapplication. The hot-melt adhesive composition was continuously appliedat a melt temperature of 180° to 200° C. into a width of 13 to 15 mm ata prescribed thickness, at the thickness of 1.5 mm unless otherwisenoted.

Non-slip processing of two-layer structure is carried out by using twogear pump type hot-melt applicators fitted with a twin coating nozzlewhich is composed of two isolated output nozzles and integrated at thetip.

Two hot-melt adhesive resin compositions are individually fed to eachoutput nozzle at temperature of 180° to 200° C. and continuously appliedto the same position so as to obtain the first coat having a width of 13to 15 mm and a thickness of 0.5±0.4 mm and the second coat (top coat)having a width of 13 to 15 mm and a thickness of 0.8±0.5 mm.

EXAMPLE 1

Ethylene-ethyl acrylate resin (hereinafter referred to as EEA) composedof 25% ethyl acrylate copolymer (Trade mark; EVAFLEX EEA A-703,manufactured by Mitsui Du Pont Polychemicals) was used, and 100 parts ofthe resin was melted at 110° C. in a nitrogen atmosphere and 12 parts of2-hydroxy-3-methacryloxypropyl phosphate was added and mixed. To theresulting mixture, 0.3 part of dicumyl peroxide was added by threeportions and a grafting reaction was carried out.

The reaction rate calculated from residual monomer ratio in themodification reaction was about 95% or more by boiling water extractionor high performance liquid chromatography. According to the results ofmeasurement by high performance liquid chromatography, at least about50% of the above phosphoric acid acrylate monomer was grafted on thestarting material resin.

After finishing modification, 35 parts of the composition thus obtainedwas mixed with the following thermoplastic polymer tackifier, wax,plasticizer and various additives to obtain a hot-melt adhesivecomposition; Melt-A as illustrated in Table 1.

    ______________________________________                                        Styrene-ethylene-butylene-styrene block                                                                 10     parts                                        copolymer resin (SEBS) having 29% styrene                                     content (Trade mark; Kraton G-1652,                                           manufactured by Shell Chemicals)                                              Hydrogenated dicyclopentadiene resin                                                                    30     parts                                        having a softening point of 105° C. (Trade                             mark, Escorez 5300, manufactured by                                           Tonex)                                                                        Rosin ester derivative (Trade mark;                                                                     10     parts                                        SUPER ESTER A-115, manufactured by                                            Arakawa Chemical)                                                             Acid modified polypropylene wax                                                                         10     parts                                        (PP wax) (Trade mark; Viscol TS-200,                                          manufactured by Sanyo Chemical                                                Industries)                                                                   Naphthene oil plasticizer 5      parts                                        Hindered phenol antioxidant (Trade                                                                      0.25   part                                         mark; IRGANOX-1010, manufactured                                              by Ciba-Geigy)                                                                Ultraviolet absorber (Trade mark;                                                                       0.25   part                                         TINUVIN-P, manufactured by                                                    Ciba-Geiby)                                                                   ______________________________________                                    

Thus-obtained hot-melt adhesive composition Melt-A had a melt viscosityof about 15,000 cps at 190° C.

Viscosity change rate after heat stability test at 190° C. for 48 hourswas 10% or less. The heat stability was good and abnormality such asskinning was not observed.

EXAMPLE 2

A hot-melt resin composition; Melt-B was prepared by carrying out thesame procedures as described in Example 1 except that2-hydroxy-3-methacryloxypropyl phosphate was replaced by2-hydroxy-3-methacryloxyethyl hosphate.

Thus-obtained adhesive composition; Melt-B had melt viscosity of 15,000cps at 190° C. Viscosity change rate after heat stability test at 190°C. for 48 hours was 10% or less. The heat stability was good andabnormality such as skinning was not observed.

EXAMPLE 3

Following materials were mixed and kneaded at 110° C.

    ______________________________________                                        EEA resin composed of 17% ethyl acrylate                                                                 25    parts                                        copolymer (Trade mark; EVAFLEX A-707,                                         manufactured by Mitsui Du Pont                                                Polychemicals)                                                                SEBS having 14% styrene content (Trade                                                                   10    parts                                        mark; Clayton G-1657, manufactured                                            by Shell Chemicals)                                                           Tackifier, hydrogenated dicyclopentadiene                                                                30    parts                                        resin having a softening point of 125° C.                              (Trade mark; Escorez 5320,                                                    manufactured by Tonex)                                                        ______________________________________                                    

To the resulting mixture, 2 parts of 2-hydroxy-3-methacryloxypropylphosphate was added in a nitrogen atmosphere and thereafter 0.5 part ofdicumyl peroxide was added by three portions to carry out a graftingreaction.

The reaction rate calculated from residual monomer ratio in eachmodification reaction was about 95% or more by boiling water extractionor high performance liquid chromatography.

The modified resin composition thus obtained was mixed with thefollowing tackifier, wax, plasticizer and various additives to obtain ahot-melt adhesive composition; Melt-C as illustrated in Table 1.

    ______________________________________                                        Rosein ester derivative (Trade mark;                                                                    15     parts                                        SUPER ESTER A-115, manufactured by                                            Arakawa Chemical)                                                             Acid modified PP wax (Trade mark;                                                                       12.5   parts                                        Viscol TS-200, manufactured by Sanyo                                          Chemical Industries)                                                          Naphthene oil plasticizer 5      parts                                        Hindered phenol antioxidant (Trade                                                                      0.25   part                                         mark; IRGANOX-1010, manufactured by                                           Ciba Geigy)                                                                   Ultraviolet absorber (Trade mark;                                                                       0.25   part                                         TINUVIN-P, manufactured by                                                    Ciba Geigy)                                                                   ______________________________________                                    

Thus-obtained hot-melt adhesive composition; Melt-C had a melt viscosityof about 8000 cps at 190° C.

Viscosity change rate after heat stability test at 190° C. for 48 hourswas 10% or less. The heat stability was good and abnormality such asskinning was not observed.

EXAMPLE 4

A hot-melt resin composition; Melt-D was obtained by carrying out thesame procedures as described in Example 3 except that2-hydroxy-3-methacryloxypropyl phosphate was replaced by2-hydroxy-3-methacryloxyethyl phosphate.

EXAMPLE 5

Following materials were mixed and kneaded at 150° C.

    ______________________________________                                        EEA composed of 25% ethyl acrylate                                                                       20 parts                                           copolymer (Trade mark; EVAFLEX A-703,                                         manufactured by Mitsui Du Pont                                                Polychemicals)                                                                Butyl rubber (Trade mark; BUTYL-365,                                                                      5 parts                                           manufactured by Japan Synthetic Rubber)                                       Mixture of styrene-ethylene-butylene                                                                     10 parts                                           copolymer (SEB) and SEBB which has 28%                                        styrene content (Trade mark; Kraton G-1726X,                                  manufactured by Shell Chemicals)                                              Hydrogenated terpene resin tackifier                                                                     40 parts                                           having softening point of 150° C.                                      (Trade mark; Clearon P-125, manufactured                                      by Yasuhara Chemical)                                                         ______________________________________                                    

To the resulting mixture, 3 parts of ethanolamine half salt of2-hydroxy-3-methacryloxypropyl phosphate were added and further 0.5 partof 2,5-dimethyl-2,5di(tert-butylperoxy)cyclohexane was added by threeportions and a grafting reaction was carried out.

The modified resin composition thus obtained was mixed with thefollowing tackifier, wax, plasticizer, pigment and various additives toobtain a hot-melt adhesive composition; Melt-E as illustrated in Table1.

    ______________________________________                                        Terpene phenol base tackifier (Trade                                                                    18     parts                                        mark; YS-POLYSTAR #2130, manufactured by                                      Yasuhara Chemical)                                                            Polyethylene wax (PE wax) (Trade mark;                                                                  3      parts                                        NEOWAX-L, manufactured by Yasuhara                                            Chemical)                                                                     Liquid polybutene plasticizer (Trade mark;                                                              5      parts                                        HV-300, manufactured by Nippon                                                Petrochemical)                                                                Hindered phenol antioxidant (Trade mark;                                                                0.3    part                                         IRGANOX-1706, manufactured by                                                 Ciba Geigy)                                                                   Tris-nony1phenyl phosphite antioxidant                                                                  0.5    part                                         Ultraviolet absorber (Trade mark; TINUVIN-P,                                                            0.25   part                                         manufactured by Ciba Geigy)                                                   Carbon black              0.02   part                                         Colloidal silica (Trade mark;                                                                           1.0    part                                         AEROSIL #200)                                                                 ______________________________________                                    

Thus-obtained hot-melt adhesive composition; Melt-E had melt viscosityof 25,000 to 27,000 cps at 190° C.

Viscosity change rate after heat stability test at 190° C. for 48 hourswas 10% or less. The heat stability was good and abnormality such asskinning was not observed at all.

EXAMPLE 6

A hot-melt resin composition; Melt-F was prepared by carrying out thesame procedures as described in Example 5 except that ethanolamine halfsalt of 2-hydroxy-3-methacryloxypropyl phosphate was replaced by ethanolamine half salt of 2-hydroxy-3-methacryloxyethyl phosphate.

EXAMPLE 7

A hot-melt resin composition; Melt-G was prepared by carrying out thesame procedures as described in Example 5 except that ethanolamine halfsalt of 2-hydroxy-3-methacryloxypropyl phosphate was replaced byacidphosphoxypolyoxyethylene glycol monomethacrylate.

EXAMPLE 8

A hot-melt resin composition; Melt-H was prepared by carrying out thesame procedures as described in Example 5 except that ethanolamine halfsalt of 2-hydroxy-3-methacryloxypropyl phosphate was replaced by acidphosphoxypolyoxypropylene glycol monomethacrylate.

EXAMPLE 9

A solution was prepared by dissolving 100 parts of the samethermoplastic resin EEA as used in Example 1 in 200 parts of a mixtureof toluene and n-hexane and heated to 110°. The resulting solution wascooled to 20° C. and 10 parts of 2-hydroxy-3-dimethacryloxypropylphosphate were added in a nitrogen atmosphere. About 1.0 part of1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane was successivelyadded by two portions to carry out a grafting reaction.

After finishing the modification reaction, solvent was completelyremoved from the reaction mixture by heating under vacuum. The residuewas converted to monoethanolamine salt and 25 parts of the modifiedresin thus obtained were mixed with the following thermoplastic basepolymer, tackifier, wax and various additives to obtain a hot-meltadhesive composition; Melt-I as illustrated in Table 1.

    ______________________________________                                        SEBS having 29% styrene content (Trade mark;                                                            10     parts                                        Kraton G-1652, manufactured by                                                Shell Chemicals)                                                              Hydrogenated C-9 base petroleum resin                                                                   10     parts                                        V (Trade mark; Arcon P-115 manufactured                                       by Arakawa Chemical)                                                          Terpene resin (Trade mark; YS-RESIN                                                                     11     parts                                        TO-115, manufactured by Yasuhara                                              Chemical)                                                                     Hydrogenated C-5/C-9 base petroleum                                                                     10     parts                                        resin (Trade mark; Adomarb S-100,                                             manufactured by Idemitsu Petrochemical)                                       Acid modified PE wax (Trade mark;                                                                       2      parts                                        HIWAX 2203A, manufactured by                                                  Mitsui Petrochemicals)                                                        PP wax (Trade mark; Viscol 660P,                                                                        15     parts                                        manufactured by Sanyo Chemical                                                Industries)                                                                   Atactic polypropylene (Trade mark;                                                                      10     parts                                        M-grade, manufactured by                                                      Mitsui Toatsu Chemicals)                                                      Liquid polybutene (Trade mark; HV-1900,                                                                 5      parts                                        manufactured by Nippon Petrochemical)                                         Butoxytriethylene glycol acid                                                                           1      part                                         phosphate                                                                     Antioxidant (Trade mark; IRGANOX-1010,                                                                  0.5    part                                         manufactured by Ciba Geigy)                                                   Tris-nonylphenyl phosphite                                                                              0.5    part                                         antioxidant                                                                   ______________________________________                                    

Thus-obtained hot-melt adhesive composition; Melt-I had a melt viscosityof about 20,000 cps at 180° C.

Viscosity change rate after heat stability test at 190° C. for 48 hourswas 10% or less. The heat stability was good and abnormality such asskinning was not observed.

EXAMPLE 10

A hot-melt resin composition; Melt-J was obtained by carrying out thesame procedures as described in Example 9 except that2-hydroxy-3-dimethacryloxypropyl phosphate was replaced by anapproximately 1:1 mixture of 2-hydroxy-3-methacryloxyethyl phosphate and2-hydroxy-3-dimethacryloxyethyl phosphate and the modified product wasconverted to a monoammonium salt.

EXAMPLE 11

A solution was prepared by dissolving 50 parts of terpene phenol resin(Trade mark; YS Polystar T-130, manufactured by Yasuhara Chemical) and50 parts of hydrogenated liquid polyisoprene diol having a hydroxylequivalent of 0.90 mg/g and an average molecular weight of 2,500 (Trademark; PIP-H, manufactured by Idemitsu Petrochemical) in 200 parts oftoluene at 20° C. To the solution obtained, 3.5 parts of phosphoruspentoxide were added by four portions. After finishing the reaction,toluene was removed. To the residue, 0.3 to 0.4 part of water was addedto carry out hydrolysis. Thus a modified resin was obtained.

According to the results of measurement by high performance liquidchromatography, at least about 95% of phosphorus pentoxide was graftedon the starting material resin.

After finishing modification, 35 parts of the modified resin were mixedwith the following thermoplastic base polymer, tackifier, wax andvarious additives to obtain a hot-melt adhesive composition; Melt-K asillustrated in Table 1.

    ______________________________________                                        Styrene-isoprene-styrene resin (SIS) having                                                             20     parts                                        14% styrene content (Trade mark;                                              Quintac 3421, manufactured by                                                 Nippon zeon)                                                                  SEBS having 14% styrene content (Trade                                                                  10     parts                                        mark; Kraton G-1657, manufactured                                             by Shell Chemicals)                                                           Rosin ester resin (Trade mark; SUPER                                                                    25     parts                                        ESTER A-115, manufactured by                                                  Arakawa Chemical)                                                             PP wax (Trade Mark; Viscol 660P,                                                                        10     parts                                        manufactured by Sanyo Chemical                                                Industries)                                                                   Antioxidant (Trade mark; IRGANOX-1010,                                                                  0.2    part                                         manufactured by Ciba Geigy)                                                   Tris-nonylphenyl phosphite antioxidant                                                                  0.5    part                                         ______________________________________                                    

Thus-obtained hot-melt adhesive composition; Melt-K had melt viscosityof about 30,000 cps at 160° C. Viscosity change rate after heatstability test at 160° C. for 48 hours was 25% or less. The heatstability was good and abnormality such as skinning was not observed.

EXAMPLE 12

A hot-melt resin composition; Melt-L was prepared by carrying out thesame procedures as described in Example 11 except that phosphoruspentoxide was replaced by 4 parts of phosphorus oxychloride.

EXAMPLE 13

A mixture composed of 60 parts of C5-C9 base hydrogenated petroleumresin tackifier (Trade mark; Admarb S-100, manufactured by IdemitsuPetrochemical), 40 parts of styrene-ethylene-propylene resin (Trademark; Kraton GX-1701, manufactured by Shell Chemicals) and 3 parts ofmaleic anhydride was melted and 0.5 part of2,5-dimethyl-2,5-di(tert-butylperoxy)hexane-3 was added to carry out agrafting reaction.

To 100 parts of the resulting resin composition obtained by introducingan acid anhydride group into the molecule, 1.8 parts of glycidol wasadded and reacted, and successively 2.5 parts of phosphorus pentoxidewas reacted to obtain a modified resin.

Eighty parts of the modified resin was mixed with the followingthermoplastic base polymer, wax and various additives to obtain ahot-melt adhesive composition; Melt-M as illustrated in Table 1.

    ______________________________________                                        SEBS (Trade mark; Taftec H-1051,                                                                        5      parts                                        manufactured by Asahi Chemical                                                Industry)                                                                     PP wax (Trade mark; Viscol 660-P,                                                                       10     parts                                        manufactured by Sanyo Chemical                                                Industries)                                                                   Liquid polybutene plasticizer                                                                           5      parts                                        (Trade mark; HV-300, manufactured by                                          Nippon Petrochemical)                                                         Antioxidant (Trade mark; IRGANOX-1010,                                                                  0.2    part                                         manufactured by Ciba Geigy)                                                   Tris-nonylphenyl phosphite antioxidant                                                                  0.5    part                                         ______________________________________                                    

Thus-obtained heat-melt adhesive composition; Melt-M had melt viscosityof about 10,000 cps at 180° C.

Viscosity change rate after heat stability test at 180° C. for 48 hourswas about 15% or less. The heat stability was good and abnormality suchas skinning was not observed.

EXAMPLE 14

A mixture composed of 35 parts of a commercial acid modified SEBS resingrafted with 2% maleic anhydride (Trade mark; Kraton RG-1901X,manufactured by Shell Chemicals) and 65 parts of hydrogenated petroleumresin base tackifier (Trade mark; Escorez 5300) was reacted with 1.1parts of glycidol and successively reacted with 2.0 parts of phosphoruspentoxide.

After finishing modification, 80 parts of the resulting modified resinwas mixed with the following thermoplastic base polymer, wax and variousadditives to obtain a hot-melt adhesive composition; Melt-N.

    ______________________________________                                        SEBS (Trade mark; Taftec H-1051,                                                                        5      parts                                        manufactured from Asahi Chemical                                              Industry)                                                                     PP wax (Trade mark; Viscol 660P,                                                                        10     parts                                        manufactured by Sanyo Chemical                                                Industries)                                                                   Liquid polybutene plasticizer (Trade                                                                    5      parts                                        mark; HV-300, manufactured by                                                 Nippon Petrochemical)                                                         Antioxidant (Trade mark; IRGANOX-1010,                                                                  0.2    part                                         manufactured by Ciba Geiby)                                                   Tris-nonylphenyl phosphite                                                                              0.5    part                                         ______________________________________                                    

COMPARATIVE EXAMPLE 1

Thirty five parts of EEA composed of 25% ethyl acrylate copolymer (Trademark; EVAFLEX A-703, manufactured by Mitsui Du Pont Polychemical) weremixed with the following thermoplastic base polymer, tackifier, wax,plasticizer and various additives to obtain a hot-melt adhesivecomposition; Melt-1 as illustrated in Table 1.

    ______________________________________                                        SEBS having 29% styrene content                                                                         10     parts                                        (Trade mark; Kraton G-1652, manufactured                                      by Shell Chemicals)                                                           Hydrogenated dicyclopentadiene resin                                                                    45     parts                                        having a softening point of 105° C. (Trade                             mark; Escolety 5300, manufactured by                                          Tonex)                                                                        Rosin ester derivative (Trade mark;                                                                     10     parts                                        SUPER ESTER A-115, manufactured by                                            Arakawa Chemical)                                                             PP wax (Trade mark; Viscol TS-200,                                                                      10     parts                                        manufactured by Sanyo Chemical                                                Industries)                                                                   Naphthene oil plasticizer 5      parts                                        Antioxidant (Trade mark; IRGANOX-1010,                                                                  0.25   part                                         manufactured by Ciba-Geigy)                                                   Ultraviolet absorber (Trade mark;                                                                       0.25   part                                         TINUVIN-P, manufactured by                                                    Ciba-Geigy)                                                                   ______________________________________                                    

COMPARATIVE EXAMPLE 2

A hot-melt adhesive composition; Melt-2 was prepared by carrying out thesame procedures as described in Example 7 except that EEA (Trade mark,EVAFLEX, A-703) was replaced by a 1:1 mixture of ethylene-vinyl acetateresin (EVA having 28% vinyl acetate content (Trade mark; EVAFLEX #250)and EVA having 19% vinyl acetate content (Trade mark; EVAFLEX #450).

COMPARATIVE EXAMPLE 3

A hot-melt adhesive composition; Melt-3 was prepared by carrying out thesame procedures as described in Example 7 except that EEA (Trade mark;EVAFLEX A-703) was replaced by a 1:1 mixture of SIS having 14% styrenecontent (Trade mark; Califlex TR-1107) and SIS having 21% styrenecontent (Trade mark; Califlex TR-1111).

COMPARATIVE EXAMPLE 4

A hot-melt adhesive composition; Melt-4 was prepared by carrying out thesame procedures as described in Example 7 except that EEA (Trade mark;EVAFLEX A-703) was replaced by a mixture consisting of 10% of butylrubber (Trade mark; JSR Butyl #365), 10% of polyisobutylene (Trade mark;VISTANEX L-80, manufactured by Exxon) and 80% of atactic polypropylenehaving a softening point of 140° C.

    TABLE 1      Example Comp. Example No.  1 2 3 4 5 6 7 8 9 10 11 12 13 14 1 2 3 4     Melt No.  A B C D E F G H I J K L M N 1 2 3 4       Condition (1), Between                IP IP IP IP SPCC oiled-face     steel adhesion  0° C. 80 77 57 59 15 16 13 13 75 83 -- -- 35 95     3.0 2.5 20 18 Tensile shear strength (kg/cm.sup.2) 20° C. 41 40     17 16 3.8 4.0 3.3 3.3 47 45 -- -- 44 46 <0.3 <0.2 <0.3 <0.2  50°     C. 3.6 3.4 2.9 3.0 0.9 0.9 0.8 0.8 6.9 9.0 -- -- 4.5 6.0 < 0.1 <0.1 <0.1     <0.1 T-peel strength (kg/in)  0° C. 18 19 12 13 6.1 6.4 5.9 5.8     14 13 -- -- 1.0 0.6 0 0 0 0  20° C. 12.5 12.3 7.1 6.8 1.2 1.3 1.0     0.9 15 16   9.0 11 <0.1 <0.1 <0.1 <0.1  50° C. 3.9 3.7 2.5 2.2     0.5 0.4 0.3 0.3 4.4 4.7   3.1 4.1 -- -- -- -- Condition (2), Oiled SPCC/                    IP IP IP IP aluminum adhesion  0° C. 89 95 61 62     16 17 14 14 91 88 4.8 4.5 38 96 3.5 3.0 11 8 Tensile shear strength     20° C. 47 48 17 18 4.1 4.3 3.5 3.4 50 49 1.7 1.8 47 50 1.1 1.3     3.0 2.5 (kg/cm.sup.2) 40° C. 12 11 6.8 7.1 1.4 1.6 1.1 1.2 20 17     0.3 0.3 4.6 16 <0.1 <0.1 <0.1 <0.1 T-peel strength (kg/in)  0°     C. 20 21 14 15 6.3 7.0 6.0 6.1 17 16 3.0 3.2 1.5 7.0 NG NG NG NG     20° C. 13.5 13.7 9.8 8.7 1.5 1.4 1.0 1.0 16 16 1.0 1.1 9.5 12     <0.2 <0.2 <0.2 <0.2  40° C. 4.0 4.1 3.1 3.3 0.8 0.7 0.6 0.6 4.7     5.0 0.3 0.3 3.1 4.5 -- -- -- -- Condition (3), Galvanized     IP IP IP IP iron/ABS adhesion 20° C. 12.7 13.3 11.2 11.5 1.0 1.1     0.9 0.9 14.0 12.4 1.1 1.3 8.5 10 <0.1 <0.1 <0.2 <0.2 T-peel strength     (kg/in) 40° C. 4.0 3.9 3.0 3.1 0.6 0.5 0.4 0.3 4.0 4.4 0.2 0.3     2.7 4.1 -- -- -- -- Condition (4), Between                IP IP IP IP     oiled stainless steel adhesion  0° C. 18 17 9.2 11 6.1 5.5 4.9     5.8 14 13 2.8 2.6 1.0 6.5 NG NG NG NG T-peel strength (kg/in) 20°     C. 12 11.7 10.7 10.5 0.9 0.8 0.7 0.8 13 12.5 0.9 0.8 6.0 4.1 <0.3 <0.2     <0.3 <0.2 Condition (5), Between SPCC                IP IP IP IP steel     adhesion, 20° C. 13.4 13.0 7.1 7.4 1.2 1.3 1.1 1.0 15 17 1.1 1.2     4.2 5.3 <0.1 <0.1 <0.1 <0.1 T-peel strength (kg/in) Condition (2), oiled     SPCC/                IP IP IP IP PP adhesion  0° C. 77 69 49 45     13 14 11 10 70 79 5.0 4.4 33 88 12 11 2.8 8.0 Tensile shear strength     (kg/cm.sup.2) 20° C. 36 35 15 15 3.6 3.6 3.5 3.6 46 45 1.7 1.6 45     48 1.0 0.5 0.6 0.3 90°-peel strength (kg/in)  0° C. 17 18     11 13 5.8 6.0 4.8 4.9 15 14 3.3 3.5 0.9 6.6 NG NG NG NG  20° C.     11 12 9.8 10 0.8 0.6 0.6 0.6 11 11.5 0.8 0.7 5.4 3.9 <0.1 <0.1 <0.1 <0.1     PP/ABS adhesion  0° C. 82 79 61 60 17 18 16 15 80 91 4.9 5.0 45     99 88 90 12 15 PC/Galvanized iron,  0° C. 74 66 54 52 13 14 12 12     69 74 4.0 4.6 39 71 10 13 3.0 8.5 condition (3) Tensile shear strength     (kg/cm.sup.2) SPCC steel plate  ⊚ ⊚     ⊚ ⊚ ⊚ ⊚     ⊚ ⊚ ⊚ ⊚     ⊚ ⊚ ⊚ ⊚ X X     Δ X Warm water corrosion Galvanized sheet iron  ⊚     ⊚ ⊚ ⊚ ⊚     ⊚ ⊚ ⊚ ⊚     ⊚ ⊚ ⊚ ⊚     ⊚ X X Δ X Warm water corrosion SPCC steel plate     ⊚ ⊚ ⊚ ⊚     ◯ ◯ ⊚ ⊚ .circleinci     rcle. ⊚ ⊚ ⊚ ◯     ◯ X X X X Salt water corrosion Galvanized sheet iron     ⊚ ⊚ ⊚ ⊚     ⊚ ⊚ ⊚ ⊚     ⊚ ⊚ ⊚ ⊚     ◯ ◯ X X X X Salt water corrosion PP/Galvanized     iron, Condition (3)  108 110 113 126 110 104 98 103 117 121 97 96 123     118 <10 <5 <10 <5 Adhesion Warm water immersion 40° C. × 5     days, Shear strength retention (%) Condition (2), SPCC/PP  110 98 124     128 108 106 107 110 122 130 101 106 110 103 <5 <5 <20 <5 Adhesion,     40° C. ×      RH 95%, 10 days Shear strength retention (%)

Remarks on Table 1

Tensile shear test was conducted at a crosshead speed of 25 mm/min.T-peel and 90°-peel test were conducted at a crosshead speed of 50mm/min.

Preparation conditions of adhered specimen

Using a hand-gun for fusing the melt sample at 180°-200° C., the Meltsample was coated on one side of a metal specimen, another specimen wasimmediately placed on the coated portion, and clamped for 2-10 secondsto complete adhesion. Adhesive thickness was adjusted to 50-150 μm. Inthe case of melt-A, B, 1 and 2 which have a relatively short open timeof 10 seconds or less, metal specimens for the test were previouslywarmed to 50°-60° C. in order to suitably carry out adhesion by handmethod. On the other hand, when adhesion was carried out without warmingunder open time of 2-3 seconds, the adhesion strength exhibited at least75% of the value illustrated in Table 1. The adhesion strength increasedwith passage of time. Consequently, previous warming is optional anddoes not limit the invention.

Description of characters

Condition (1) ... Submerging treatment is press oil and rust prooflubricant.

Condition (2) ... Submerging treatment in an emulsion type lubricantprimarily containing mineral oil.

Condition (3) ... Submerging treatment in an emulsion type lubricantprimarily containing vegetable oil.

Condition (4) ... Spray coating treatment with rust proof lubricant 5-56(manufactured by Kure Industry), allowing to stand for 1 day and wipingoff excess oil.

Condition (5) ... Intact oil-treated specimen purchased from Nippon TestPanel.

PP ... Polypropylene plate 25×75×5 mm in dimension.

PC ... Polycarbonate plate 25×75×5 mm in dimension.

Shear strength retention (%) ... ##EQU1## NG ... Specimen was peeledbefore measurement. IP ... Complete interfacial peeling on the metalsurface.

Corrosion test

⊚ ... Rust was found only on the metal-exposed portion, and no rust wasobserved on the film-coated portion.

◯ ... Rust was found within about 1 mm in the vicinity of crosscut, andno blister or separation was observed on other coated surface.

Δ ... Rust and separation were found within about 5 mm in the vicinityof crosscut, or coated film was partly lifted or separated and rust wasobserved.

X ... Coated film was wholely separated, or rust was observed on metalexposed portion and overall film-separated portion.

Effect

As clearly seen in Table 1, the hot-melt adhesive compositions incomparative examples exhibited very low adhesive strength or incompleteadhesion, low T-peel strength in particular, and caused interfacialpeeling on the metal surface, in all cases, without exerting oiled-faceadhesion. These results illustrated very large effect of oil.

These phenomenons are reasonably considered that the oil existing on themetal surface extremely inhibits required property for adhesion, thatis, wettability or affinity of the adhesive composition to the metalsurface.

Comparative examples also led to severe decrease in strength in agingtest and practical use of these compositions were thought to bedifficult.

On the other hand, the oiled-face adherable, hot-melt adhesivecomposition of the invention has proved to exhibit excellent oiled-faceadhesion as seen in the examples illustrated in Table 1.

The oiled-face adherable, hot-melt resin compositions, Melt A to Melt N,in the invention increased their adhesive strength after aging due tocuring effect.

The oiled-face adherable hot-melt resin composition was simultaneouslyfound to have a remarkable effect on rust proof. No development of rustwas observed particularly in the immersion into warm water or saltwater.

The hot-melt adhesive compositions described in examples 1-5 had an opentime of from 15 to 30 seconds and a setting time of about 15 seconds orless to perform complete adhesion. Thus high workability andproductivity has been confirmed.

That is, the novel hot-melt resin composition obtained by introducingthe phosphoric acid group or a combination of the phosphoric acid groupand the (dehydrated) carboxyl group into one or more molecular chains inthe constitutive components of the hot-melt adhesive composition canprovide the following characteristics.

It has been found to provide a quite novel characteristic for adheringan oil-stained metal surface in addition to instant adhesion freedomfrom pollution and heat stability for a long time which arecharacteristics of the hot melt resin composition. Further, adhesion toplastics which are difficult to adhere and rust inhibiting property havealso been exhibited.

Consequently, the present invention provides a novel and highly reliablehot-melt adhesive composition which retains instant adhesion and freedomfrom pollution, has excellent adhesion to oiled surface and dominantrust proof property, and is most suitable for use in adhesion and sealof metals with various plastics and other materials. The adhesivecomposition can be preferably used for adhesion of metals with eachother, plastics with each other, lamination or adhesion and sealing ofvarious plastics and metals, metal protective coating, non-sliptreatment on metal surface and adhesion of metals with differentmaterials.

EXAMPLE 15

Melt-A obtained in Example 1 was applied by one layer hot-melt method toan untreated scaffolding board so as to obtain an average film thicknessof 1.5 mm. This is referred to as Example 15-1.

Another non-slip treated scaffolding board was obtained by conductingthe same procedures as carried out in Example 15-1 except that Melt-Awas replaced by Melt-B obtained in Example 2. This is referred to asExample 15-2.

The non-slip properties of the scaffolding boards obtained in Examples15 -1 and 15-2 were measured in accordance with JIS K-7204. After 1000rotations of truck wheel No. CS-17 under 1 kg load, abrasion wear was 10mg or less and almost no abrasion was observed.

The sliding friction test at room temperature in accordance with ASTMD-1894-63 exhibited a sliding angle of 50 to 55 degrees which was a goodanti-slip property.

The non-slip treated board obtained in Example 15-1 was allowed to standat 35° C. under pressure of 0.5 kg/cm² for 3 days to observe blockingproperty. After the test, little blocking was found and there was quiteno problem for actual use.

A small piece was cut out from the coated portion of the non-sliptreated scaffolding board and submerged in warm water at 40° C. for 10days. The adhesive strength of the coated film increased afterimmersion.

Adhesion of the non-slip coated film of the scaffolding boards obtainedin Examples 15-1 and 15-2 were satisfactory for practical use.

EXAMPLE 16

Melt-A obtained in Example 1 and Melt-5 obtained by below describedprocess were applied for coating an untreated scaffolding board. Melt-Awas directly applied to the board as a primary layer with a thickness of0.5 mm. Melt-5 was applied to form a top a top layer with a thickness ofabout 0.8 mm. Wet-on-wet coating was carried out through a complexnozzle-die at a line speed of 15 m/min by using two hot-meltapplicators.

The above hot-melt resin composition; Melt-5 has the followingcomposition.

    ______________________________________                                        Ethylene-vinyl acetate resin having 19% vinyl                                                            30     parts                                       acetate content (Trade mark; EVAFLEX #450,                                    manufactured by Mitsui Du Pont                                                Polychemicals)                                                                Sytrene-butadiene-styrene resin                                                                          5      parts                                       having 30% styrene content (Trade                                             mark; Califlex TR-1101, manufactured                                          by Shell Chemicals)                                                           Rosin ester resin (Trade mark; SUPER ESTER                                                               25     parts                                       A-115, manufactured by Arakawa                                                Chemical)                                                                     Hydrogenated dicyclopentadiene resin                                                                     20     parts                                       (Trade mark; Escorez 5300, manufactured                                       by Tonex)                                                                     PE wax (Trade mark; NEOWAX-L, manufactured                                                               19.8   parts                                       by Yasuhara Chemical)                                                         Antioxidant (Trade mark; IRGANOX-1010,                                                                   0.2    part                                        manufactured by Ciba Geigy)                                                   ______________________________________                                    

Non-slip property was measured on the next day.

After 1000 rotations in the non-slip property test, abrasion wear wasabout 50 mg or less and a sliding angle of 40 to 45 degrees was obtainedin the sliding friction test. Good anti-slip properties were obtained.

The non-slip treated scaffolding board was allowed to stand at 40° C.under pressure of 1.5 kg/cm² for 3 days and blocking property wasobserved. Blocking was little and no problem was found for actual use.Blocking indicated by separation strength was 0.15 kg per 30 cm lengthof the scaffolding board.

The T-peel strength of the double-layer film composed of Melt-A andMelt-5 was 7.5 kg/in or more at 20° C., and 2.8 kg/in or more at 50° C.

A test piece of 15 cm in length was cut out from the non-slip treatedscaffolding board and submerged in warm water at 40° C. for 10 days. Theadhesive strength of the coated film increased after immersion. Thusadhesion the non-slip layer of the scaffolding board was satisfactoryfor practical use.

COMPARATIVE EXAMPLE 5

EEA composed of 25% ethyl acrylate copolymer (Trade mark; EVAFLEX A-703,manufactured by Mitsui Du Pont Polychemicals) was used and 35 parts ofEEA were mixed with the following thermoplastic base polymer, tackifier,wax, plasticizer and other additives to prepare a hot-melt adhesivecomposition; Melt-6.

    ______________________________________                                        SEBS having 29% styrene content (Trade                                                                  10     parts                                        mark; Kraton G-1652, manufactured                                             by Shell Chemicals)                                                           Hydrogenated dicyclopentadiene resin                                                                    45     parts                                        having a softening point of 105° C.                                    (Trade mark; Escorez 5300, manufactured                                       by Tonex)                                                                     Rosin ester derivative (Trade mark;                                                                     10     parts                                        SUPER ESTER A-115, manufactured by                                            Arakawa Chemical)                                                             PP wax (Trade mark; Viscol TS-200,                                                                      10     parts                                        manufactured by Sanyo Chemical                                                Industries)                                                                   Naphthene oil plasticizer 5      parts                                        Antioxidant (Trade mark; IRGANOX-1010,                                                                  0.25   part                                         manufactured by Ciba Geigy)                                                   Ultraviolet absorber (Trade mark;                                                                       0.25   parts                                        TINUVIN-P, manufactured by                                                    Ciba Geigy)                                                                   ______________________________________                                    

Thus-obtained hot-melt adhesive composition; Melt-6 was applied onelayer to a metal scaffolding board so as to obtain a thickness of 1.2 mmand non-slip property was measured next day. The coated film was liftedand could be readily peeled with fingers. No adhesion was found at alland favorable non-slip property was not exhibited.

The above untreated metal scaffolding board was pretreated with a gasflame to carry out degreasing and preheating. Melt-6 was applied onelayer to the board at the metal surface temperature of 200 to 270° C. soas to obtain an average thickness of 1.3 mm. The applied board wasimmediately cooled with water. The obtained board was subjected toproperty measurement next day.

The treated scaffolding board was allowed to stand at 35° C. underpressure of 1.5 kg/cm² for 3 days. Blocking was little and no problemwas found for practical use.

However, 90 degrees peel strength of Melt-6 was 4.5 kg/in in average at20° C. and caused severe decrease after submerging in warm water at 40°C. for 10 days. Most of the coated film was readily peeled with fingers.Thus treated scaffolding board was lacking in reliability for practicaluse.

What is claimed is:
 1. An oiled-face adherable, hot-melt adhesivecomposition having constitutive components comprising a thermoplasticbase polymer, tackifier and one or more of additives selected from thegroup consisting of waxes and plasticizers, one or more of molecularchains in said constitutive components comprising a modified resincomponent obtained by introducing into a molecular chain a functionalgroup represented by the formula (I): ##STR5## wherein R₁ is a hydrogenatom, an alkyl group having from 1 to 8 carbon atoms, ##STR6## R₂ is ahydrogen atom, methyl group, ·NH₄ or NH₃ --CH₂ --CH₂ OH; R₃ is ahydrogen atom or a methyl group; A is ##STR7## m is an integer of 2 or3; R₄ is a hydrogen atom or a methyl group; R₅ is a hydrogen atom, amethyl group, hydroxymethyl group or a chloromethyl group; X is--P--(OH)₂ ; and Y is an integer of from 1 to
 15. 2. The hot-meltadhesive composition of claim 1 wherein one or more of the molecularchain in the constitutive components comprises in the same or differentmolecular chain the phosphoric acid group represented by the formula (I)in claim 1 or an half amine salt of the same and further one or morefunctional groups selected from --COOH or ##STR8##
 3. The adhesivecomposition of claim 2 wherein the constitutive components comprise amodified resin component obtained by grafting an unsaturated carboxylicacid or an unsaturated carboxylic acid anhydride in an amount of 5% byweight or less.
 4. The adhesive composition of claim 1 wherein thetackifier comprises one or more materials selected from the groupconsisting of hydrogenated rosin, hydrogenated rosin ester derivativeand polymerized rosin in an amount of from 1 to 40% by weight.
 5. Theadhesive resin composition of claim 1 wherein the constitutivecomponents comprise a modified resin component obtained by grafting from0.1 to 20 parts by weight of a compound selected from2-hydroxy-3-(meth)acryloxypropyl phosphate,2-hydroxy-3-(meth)acryloxyethyl phosphate or an half amine salt of thesame into 100 parts by weight of the constitutive components.
 6. Theadhesive composition of claim 1 wherein the constitutive componentscomprise a modified resin component obtained by reacting a resincomponent having a hydroxyl group with an agent selected from the groupconsisting of phosphorus pentoxide, phosphorus trichloride andphosphorus oxychloride, and hydrolyzing the resultant intermediate. 7.The adhesive composition of claim 1 wherein the constitutive componentscomprise a modified resin component obtained by introducing a glycidylgroup into the constitutive components and successively reacting withphosphorous acid or phosphoric acid.
 8. The adhesive composition ofclaim 1 wherein the constitutive components comprise one or more ofthermoplastic resin having a molecular weight in the range of from20,000 to 1,000,000 and selected from the group consisting ofstyrene-ethylene-butylene-styrene resin, styrene-ethylene-butyleneresin, styrene-ethylenepropylene-styrene resin, ethylene-propyleneresin, and ethylene-acrylate ester resin; and the thermoplastic resinpreviously comprises one or both of the modified resin componentsobtained by (A) grafting from 1 to 20 parts by weight of a compoundselected from the group consisting of 2-hydroxy-3-(meth)acryloxypropylphosphate, 2-hydroxy-3-(-meth)acryloxyethyl phosphate and an half aminesalt of the same upon 100 parts by weight of the thermoplastic resin, orby (B) grafting from 0.1 to 5 parts by weight of a monomer selected frommaleic anhydride, acrylic acid and methacrylic acid.
 9. The adhesivecomposition of claim 1 wherein the constitutive components are composedof:(a) from 5 to 80% by weight of two or more of thermoplastic resinhaving a molecular weight of from 20,000 to 1,000,000 and selected fromthe group consisting of butyl rubber, polyisobutylene,styrene-butadiene-styrene resin, styrene-isoprene-styrene resin,styrene-ethylene-butylene styrene resin, styrene-ethylene-butyleneresin, styreneethylene-propylene-styrene resin, ethylene-propyleneresin, ethylene-vinyl acetate resin and ethylene-acrylate ester resin,(b) from 20 to 60% by weight of one or more of tackifier selected fromthe group consisting of a hydrogenated terpene base resin, hydrogenatedpetroleum resin, hydrogenated alicyclic base petroleum resin and a rosinester derivative resin, (c) from 1 to 20% by weight of one or more ofwax selected from the group consisting of paraffin base wax,polyethylene base wax, polypropylene base wax and modified waxesthereof, and (d) from 0 to 30% by weight of one or more of plasticizerselected from the group consisting of liquid polybutene, liquidhydrogenated polyisoprene and atactic polypropylene; and saidconstitutive components comprise a modified resin component obtained bygrafting from 1 to 20 parts by weight of2-hydroxy-3-(meth)acryloxypropyl phosphate or2-hydroxy-3-(meth)acryloxyethyl phosphate upon 100 parts by weight ofthe sum of the thermoplastic resin and one or more of other constitutivecomponents.
 10. A non-slip processing method of a metal scaffoldingboard comprising conducting hot-melt coating of an oiled-face adherable,hot-melt adhesive composition of claim 1 on the back surface of themetal scaffolding board without surface treatment in a width of from 5to 30 mm.
 11. A non-slip processing method of claim 10 wherein thehot-melt coating is carried out to form a plurality of coated layer andto apply wet-on-wet to the second or the upper layer, simultaneouslywith the first layer or separately, a non polar hot-melt compositionconsisting essentially of from 20 to 60% by weight of an ethylenevinylacetate resin or an ethylene-acrylate ester resin, from 75 to 10% byweight of a tackifier having a softening point temperature of from 80°to 130° C. and from 5 to 30% by weight of a wax having a melting pointtemperature of from 100° to 150° C.